CN101225215A - Hydrogel-containing unsaturated polyester resin flame-retardant composite material and preparation method thereof - Google Patents
Hydrogel-containing unsaturated polyester resin flame-retardant composite material and preparation method thereof Download PDFInfo
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- CN101225215A CN101225215A CNA2007101152552A CN200710115255A CN101225215A CN 101225215 A CN101225215 A CN 101225215A CN A2007101152552 A CNA2007101152552 A CN A2007101152552A CN 200710115255 A CN200710115255 A CN 200710115255A CN 101225215 A CN101225215 A CN 101225215A
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- unsaturated polyester
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- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 93
- 239000000017 hydrogel Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000003063 flame retardant Substances 0.000 title claims abstract description 32
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 239000000839 emulsion Substances 0.000 claims abstract description 34
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 30
- 238000004945 emulsification Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229920006305 unsaturated polyester Polymers 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 11
- 238000007872 degassing Methods 0.000 claims description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229960004418 trolamine Drugs 0.000 claims description 8
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 7
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 229940047670 sodium acrylate Drugs 0.000 claims description 7
- -1 TX-10 Chemical compound 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004159 Potassium persulphate Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000006392 deoxygenation reaction Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000005034 decoration Methods 0.000 abstract description 3
- 239000011152 fibreglass Substances 0.000 abstract description 3
- 239000006260 foam Substances 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract description 2
- 239000007767 bonding agent Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 8
- 239000000499 gel Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011285 coke tar Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011391 polyester concrete Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- SKMHHHHLLBKNKR-UHFFFAOYSA-M sodium;prop-2-enamide;prop-2-enoate Chemical compound [Na+].NC(=O)C=C.[O-]C(=O)C=C SKMHHHHLLBKNKR-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Abstract
The invention relates to a composite flame retardant material of hydrogel unsaturated polyester resin and the preparation method. The preparation materials comprise unsaturated polyester resin 100, emulsifier 0-20, solidifying agent 0.5-3, promoter 0.05-1.5, initiator 0.02-2, cross-bonding agent 0.05-5, water-soluble monomer 1-50, and water 50 -100 in mass percent. The preparation method comprises the steps of dissolving the cross-bonding in the solution of water soluble monomer and inputting nitrogen and avoiding oxygen for 30 minutes, then filtering; dissolving the initiator and the emulsifier in the filtered solution; emulsification of hydrogel unsaturated polyester resin; adding solidifying agent and promoter to the unsaturated polyester resin emulsion to solidify. The composite flame retardant material of hydrogel unsaturated polyester resin has the advantages of high and stable preserving water rate, good flame retardant capability and dimensional stability, improving the fracture elongation and toughness, uneasy cracking, good mechanical properties, and the surface is uneasy cracking when heated or combusted. The material can be widely used in artificial timber and tar filtering, foam, thermal insulation for buildings, decoration, glass fiber reinforced plastic and other materials.
Description
Technical field
The invention belongs to polymkeric substance and technical field of composite materials, more particularly relate to the improvement and the innovation of hydrogel-containing unsaturated polyester resin flame-retardant composite material and preparation method thereof.
Background technology
In recent years, continuous progress along with industrial technology, performance requriements to novel material is more and more higher. and especially to some certain material, require to have special performances, this just needs the researchist constantly to explore new material or general purpose material is carried out modification to satisfy the demands.In great majority research, the latter's method often can comparatively fast realize.
The high comprehensive performance of unsaturated polyester resin is shaped variation and is widely used.It is mainly used in glass reinforced plastic, and next is used for casting matrix, anchoring agent, coating, artwork, insulating material and home decoration material etc.When reality is used, in unsaturated polyester, add filler usually, wait as lime carbonate, aluminium hydroxide, talcum powder, calcium sulfate, fire retardant, anti-shrinking medium and toughner and improve its performance.But because resin viscosity is big, fill volume is low, and difficulty etc. relatively during the filler fusion is used the restriction that is subjected to a certain degree.Wherein the flame retardant type unsaturated polyester uses halogen-containing or phosphorus flame retardant usually.These fire retardants generally exist cost height, burning back to produce shortcomings such as toxic substance.
At the problems referred to above, moisture unsaturated polyester resin has appearred in the later stage fifties, and can be that body structure obtains by thermal initiation, the initiation of room temperature oxidation-reduction or radiation-initiated polymerization.It has that cost is low, curing exotherm is few, volumetric shrinkage is little, flame retardant properties is good and advantage such as easy-formation processing.But moisture unsaturated polyester resin also has many weak points: the first, and moisture unsaturated polyester water retention is lower, places the air can be with the fast speed dehydration for a long time, thereby weakens or lose fire retardancy, causes dimensional contraction simultaneously.The second, though have tangible flame retardant properties under the high-moisture percentage situation, too high water ratio causes material mechanical performance significantly to descend.The 3rd, along with the raising of water ratio, elongation at break sharply reduces, and causes material fragility to become big, easily cracking.The 4th, the situation that material is heated or be full of cracks appears in burning time surface does not easily improve.These problems have hindered the practical application of moisture unsaturated polyester resin greatly.
Summary of the invention
Purpose of the present invention just is to overcome above-mentioned shortcoming and defect, and a kind of hydrogel-containing unsaturated polyester resin flame-retardant composite material and preparation method thereof is provided.It makes the unsaturated polyester ester blend have higher water retention, makes matrix material place air to keep stable water ratio, good fire retardancy and dimensional stability for a long time; Improve elongation at break, the toughness of matrix material, made material be not easy cracking, had more excellent mechanical property; Material be heated or when burning the surface be full of cracks does not appear, further improved its limiting oxygen index(LOI).
In order to achieve the above object, the present invention includes moisture unsaturated polyester resin.Its mass parts component is as follows: unsaturated polyester resin 100, emulsifying agent 0-20, unsaturated polyester solidifying agent 0.5-3, unsaturated polyester promotor 0.05-1.5, aqueous polymerization initiator 0-2, aqueous polymerization linking agent 0-5, water-soluble monomer 1-50, water 50-100.Wherein unsaturated monomer solution is made up of the unsaturated monomer that can carry out radical polymerization and initiator, linking agent, water and emulsifying agent, and the quality percentage composition of unsaturated monomer is 1-50% in the unsaturated monomer solution.
Above-mentioned water-soluble monomer is one or more the monomeric mixtures among sodium acrylate, vinylformic acid, acrylamide, methylene-succinic acid, MALEIC ANHYDRIDE, 2-acrylamido-2 methyl propane sulfonic acid AMPS or the methylacryoyloxyethyl trimethyl ammonium chloride DMC.The sodium acrylate effect is best.
Emulsifying agent is that in SPAN-60, SPAN-80, SPAN-85, TWEEN-80, TX-10, trolamine, sodium hydroxide, the magnesium oxide one or more are united use.SPAN-80 and TX-10 or SPAN-80 and trolamine effect are best.
The aqueous polymerization initiator is a kind of of Potassium Persulphate, ammonium persulphate, Sodium Persulfate.The Potassium Persulphate effect is best.
The aqueous polymerization linking agent is a N,N methylene bis acrylamide.
Solidifying agent is dibenzoyl peroxide or diphenyl peroxide ketone, is preferably dibenzoyl peroxide.Promotor is N, accelerine, cobalt naphthenate one or both of mixture.N, the accelerine effect is best.
Unsaturated polyester resin is various commercially available industrialization products, generally contains the vinylbenzene of 34%-36% quality percentage composition.
The preparation method of hydrogel-containing unsaturated polyester resin flame-retardant composite material comprises the steps:
(1) linking agent is dissolved in the aqueous solution of water-soluble monomer, logical simultaneously nitrogen deoxygenation 30 minutes filters; In the solution after filtering, must concentration be the water-soluble monomer aqueous solution of 1-50% with initiator and emulsifiers dissolve again;
(2) emulsification of hydrogel-containing unsaturated polyester resin: in unsaturated polyester resin, the unsaturated water-soluble monomer aqueous solution that (1) is prepared slowly adds in the unsaturated polyester resin, carries out emulsification with high-shearing dispersion emulsifying machine simultaneously with emulsifiers dissolve;
(3) curing of hydrogel-containing unsaturated polyester resin: in the unsaturated polyester resin emulsion, add solidifying agent and promotor curing, unsaturated polyester resin composite material after solidifying placed under room temperature or 50-70 ℃ of temperature continue reaction 1-5 hour, obtain the hydrogel-containing unsaturated polyester resin matrix material.
Also through the degassing, the degassing is to adopt ultrasonic degas or vacuum outgas to above-mentioned steps (3) before curing.Solidification value is 20-35 ℃, and be 5-20 minute set time.
Water-soluble monomer in the inverse emulsion utilizes curable unsaturated polyester generation heat that cross-linking polymerization takes place simultaneously.
The present invention is that the hydrogel that utilizes the aqueous solution emulsification of unsaturated water-soluble monomer and curing back to generate carries out modification, utilizes unsaturated polyester resin curing generation heat to make the unsaturated monomer water-soluble monomer in the emulsion that cross-linking polymerization take place simultaneously unsaturated polyester resin.
Task of the present invention comes to this and finishes.
Utilize unsaturated polyester resin to solidify the generation heat and make the unsaturated monomer water-soluble monomer in the emulsion that cross-linking polymerization take place simultaneously, simplified service routine, improved operating efficiency.At first, because the moisture in the blend exists with the form of the water-sol, thereby makes the unsaturated polyester ester blend have higher water retention, make matrix material place air to keep stable water ratio for a long time, thereby keep certain fire retardancy, keep dimensional stability simultaneously.Secondly, because hydrogel has certain mechanical strength, especially when hydrogel content is higher, have better mechanical property, cause some mechanical property of matrix material to have variation more by a small margin and improve the other mechanical property with the increase of hydrogel content.The 3rd, because the existence of hydrogel improves the elongation at break of matrix material, improve toughness, make material be not easy cracking, this has more importantly meaning for the large-scale foundry goods that waters.The 4th, material be heated or when burning the surface situation about chapping does not appear, can further improve limiting oxygen index(LOI).The 5th, because the existence of hydrogel, the incendiary charring rate improves, thereby has improved limiting oxygen index(LOI).The 6th, because the interfacial characteristics between the difference of the interfacial characteristics between hydrogel and the unsaturated polyester and water and unsaturated polyester makes hydrogel-containing unsaturated polyester resin have certain light transmission.
Utilize the aqueous solution emulsification of unsaturated water-soluble monomer and solidify the hydrogel that the back generates unsaturated polyester resin is carried out modification, realized flame retardant properties, mechanical property, water retention, dimensional stability and light transmission etc. that more moisture unsaturated polyester composite has improved.Can be widely used in aspects such as imitation wood, cigarette coke tar filtration, foam article, material of construction, thermal insulating material, finishing material, polyester concrete, glass fiber infiltration agent, reactive micro-gel and coating.
Embodiment
Embodiment 1.A kind of hydrogel-containing unsaturated polyester resin flame-retardant composite material.Comprise moisture unsaturated polyester resin.
Its mass parts component is as follows: unsaturated polyester resin 100, emulsifying agent 11, unsaturated polyester solidifying agent 2.5, unsaturated polyester promotor 1.5, aqueous polymerization initiator 2, aqueous polymerization linking agent 3, water-soluble monomer 35, water 80.Wherein unsaturated monomer solution is made up of the unsaturated monomer that can carry out radical polymerization and initiator, linking agent, water and emulsifying agent, and the quality percentage composition of unsaturated monomer is 35% in the unsaturated monomer solution.
Above-mentioned water-soluble monomer is a sodium acrylate.The aqueous polymerization initiator is a Potassium Persulphate.The aqueous polymerization linking agent is a N,N methylene bis acrylamide.Emulsifying agent is SPAN-80 and TX-10.Effect is best.
Solidifying agent is a dibenzoyl peroxide, and promotor is N, accelerine, and effect is best.
Unsaturated polyester resin is various commercially available industrialization products, generally contains the vinylbenzene of 34%-36% quality percentage composition.
Embodiment 2.A kind of hydrogel-containing unsaturated polyester resin flame-retardant composite material.Comprise moisture unsaturated polyester resin.Its mass parts component is as follows: unsaturated polyester resin 100, unsaturated polyester solidifying agent 3, unsaturated polyester promotor 0.05, aqueous polymerization initiator 2, aqueous polymerization linking agent 5, water-soluble monomer 1, water 100.Wherein unsaturated monomer solution is made up of the unsaturated monomer that can carry out radical polymerization and initiator, linking agent, water and emulsifying agent, and the quality percentage composition of unsaturated monomer is 1% in the unsaturated monomer solution.
Above-mentioned water-soluble monomer is a vinylformic acid.The aqueous polymerization initiator is an ammonium persulphate.The aqueous polymerization linking agent is a N,N methylene bis acrylamide.
Emulsifying agent is SPAN-80 and trolamine, and effect is best.Solidifying agent is a diphenyl peroxide ketone.Promotor is cobalt naphthenate.
Unsaturated polyester resin is various commercially available industrialization products, generally contains the vinylbenzene of 34%-36% quality percentage composition.
Embodiment 3.A kind of hydrogel-containing unsaturated polyester resin flame-retardant composite material.Comprise moisture unsaturated polyester resin.Its mass parts component is as follows: unsaturated polyester resin 100, emulsifying agent 20, unsaturated polyester solidifying agent 0.5, unsaturated polyester promotor 1, aqueous polymerization initiator 0.02, aqueous polymerization linking agent 0.05, water-soluble monomer 50, water 50.Wherein unsaturated monomer solution is made up of the unsaturated monomer that can carry out radical polymerization and initiator, linking agent, water and emulsifying agent, and the quality percentage composition of unsaturated monomer is 50% in the unsaturated monomer solution.
Above-mentioned water-soluble monomer is acrylamide, methylene-succinic acid, three kinds of monomeric mixtures of MALEIC ANHYDRIDE.The aqueous polymerization initiator is a Sodium Persulfate.The aqueous polymerization linking agent is a N,N methylene bis acrylamide.
Emulsifying agent is that SPAN-85, TWEEN-80, sodium hydroxide are united use.Solidifying agent is a dibenzoyl peroxide, and effect is best.Promotor is N, accelerine, the two mixture of cobalt naphthenate.
Unsaturated polyester resin is various commercially available industrialization products, generally contains the vinylbenzene of 34%-36% quality percentage composition.
Embodiment 4.A kind of preparation method of hydrogel-containing unsaturated polyester resin flame-retardant composite material comprises the steps:
(1) linking agent is dissolved in the aqueous solution of water-soluble monomer, logical simultaneously nitrogen deoxygenation 30 minutes filters; Again with in initiator and the emulsifiers dissolve solution after filtering, concentration is 50% the water-soluble monomer aqueous solution;
(2) emulsification of hydrogel-containing unsaturated polyester resin: in unsaturated polyester resin, the unsaturated water-soluble monomer aqueous solution that (1) is prepared slowly adds in the unsaturated polyester resin, carries out emulsification with high-shearing dispersion emulsifying machine simultaneously with emulsifiers dissolve;
(3) curing of hydrogel-containing unsaturated polyester resin: in the unsaturated polyester resin emulsion, add solidifying agent and promotor curing, unsaturated polyester resin composite material after solidifying placed under room temperature or 50 ℃ of temperature continue reaction 5 hours, obtain the hydrogel-containing unsaturated polyester resin matrix material.
The said initiator concentration of step (1) is 0.02%%.The concentration of the said emulsifying agent of step (2) is 20%.
Also through the degassing, the degassing is to adopt ultrasonic degas or vacuum outgas to step (3) before curing, and solidification value is 20 ℃, and be 20 minutes set time.
Water-soluble monomer in the inverse emulsion utilizes curable unsaturated polyester generation heat that cross-linking polymerization takes place simultaneously.
Embodiment 5.A kind of preparation method of hydrogel-containing unsaturated polyester resin flame-retardant composite material comprises the steps:
(1) linking agent is dissolved in the aqueous solution of water-soluble monomer, logical simultaneously nitrogen deoxygenation 30 minutes filters; Again with in initiator and the emulsifiers dissolve solution after filtering, concentration is 1% the water-soluble monomer aqueous solution;
(2) emulsification of hydrogel-containing unsaturated polyester resin: in unsaturated polyester resin, the unsaturated water-soluble monomer aqueous solution that (1) is prepared slowly adds in the unsaturated polyester resin, carries out emulsification with high-shearing dispersion emulsifying machine simultaneously with emulsifiers dissolve;
(3) curing of hydrogel-containing unsaturated polyester resin: in the unsaturated polyester resin emulsion, add solidifying agent and promotor curing, unsaturated polyester resin composite material after solidifying placed under room temperature or 70 ℃ of temperature continue reaction 1 hour, obtain the hydrogel-containing unsaturated polyester resin matrix material.
The said initiator concentration of step (1) is 2%, and the concentration of emulsifying agent is 5%.
Also through the degassing, the degassing is to adopt ultrasonic degas or vacuum outgas to step (3) before curing, and solidification value is 35 ℃, and be 5 minutes set time.
Water-soluble monomer in the inverse emulsion utilizes curable unsaturated polyester generation heat that cross-linking polymerization takes place simultaneously.
Embodiment 6.A kind of preparation method of hydrogel-containing unsaturated polyester resin flame-retardant composite material comprises the steps:
(1) linking agent is dissolved in the aqueous solution of water-soluble monomer, logical simultaneously nitrogen deoxygenation 30 minutes filters; Again with in initiator and the emulsifiers dissolve solution after filtering, concentration is 35% the water-soluble monomer aqueous solution;
(2) emulsification of hydrogel-containing unsaturated polyester resin: in unsaturated polyester resin, the unsaturated water-soluble monomer aqueous solution that (1) is prepared slowly adds in the unsaturated polyester resin, carries out emulsification with high-shearing dispersion emulsifying machine simultaneously with emulsifiers dissolve;
(3) curing of hydrogel-containing unsaturated polyester resin: in the unsaturated polyester resin emulsion, add solidifying agent and promotor curing, unsaturated polyester resin composite material after solidifying placed under room temperature or 60 ℃ of temperature continue reaction 3 hours, obtain the hydrogel-containing unsaturated polyester resin matrix material.
The said initiator concentration of step (1) is 1%, and the concentration of emulsifying agent is 4%.The concentration of the said emulsifying agent of step (2) is 15%.
Also through the degassing, the degassing is to adopt ultrasonic degas or vacuum outgas to step (3) before curing, and solidification value is 30 ℃, and be 10 minutes set time.
Water-soluble monomer in the inverse emulsion utilizes curable unsaturated polyester generation heat that cross-linking polymerization takes place simultaneously.
The material of embodiment 1～6 has high and stable water retention, good fire retardancy and dimensional stability, has improved elongation at break and toughness, and is not easy to crack, good mechanical performance, be heated or when burning the surface do not chap.Can be widely used in the materials such as imitation wood and tar filtration, foam, Building Heat insulation, decoration, glass reinforced plastic.Can be widely used in various in.
Embodiment 7.A kind of preparation method of hydrogel-containing unsaturated polyester resin flame-retardant composite material, step is as follows:
Being formulated as follows of the unsaturated water-soluble monomer aqueous solution:
Preparation 66ml mass percentage concentration is 35% the sodium acrylate aqueous solution, and to wherein adding 0.265g linking agent N,N methylene bis acrylamide, stirring and dissolving feeds high purity nitrogen 30min simultaneously to get rid of the oxygen in the solution.Dissolving after-filtration solution adds initiator potassium persulfate 0.0797g, stirring and dissolving again in solution.In solution, add 1.16gTX-10, stirring and dissolving again.
The emulsification of unsaturated polyester resin and solidify as follows:
Take by weighing the 154g unsaturated polyester, make it to react completely, add 4.62gSPAN-80 again, stir with the unsaturated polyester carboxyl terminal to wherein adding the stirring of 7.7g trolamine.The unsaturated water-soluble monomer aqueous solution that has prepared is slowly poured in the unsaturated polyester, constantly stirred with glass stick simultaneously, make the aqueous solution and unsaturated polyester form emulsion.The high-shear emulsion machine of using 10000r/min was to the further emulsification 3-5 of emulsion minute, in this emulsion process because the big mulser rotating speed of emulsion viscosity height, cause emulsion constantly to heat up, need to insert the thermometer monitoring and make emulsion temperature be no more than 50 ℃, avoid monomer in the aqueous solution to react too early and form hydrogel.After emulsification finishes,, and be cooled to room temperature with the bubble in the ultrasonic wave eliminating emulsion.Add the 7.7g benzoyl peroxide and stick with paste (50% mass concentration), dissolving stirs, add 1.6gN again, accelerine solution (20% mass concentration) stirs, slowly water and cast from the silicon rubber mould, this process should prevent to bubble and produce, and is placed on sheet glass to begin on the mould to solidify 24 hours.The aqueous gel unsaturated polyester that taking-up has cured places 60 ℃ of baking ovens to make water residual monomer complete reaction in 4 hours.Make hydrogel-containing unsaturated polyester resin composite sample HCUP-1.
Embodiment 8.A kind of preparation method of hydrogel-containing unsaturated polyester resin flame-retardant composite material, step is as follows:
1, the preparation of the unsaturated water-soluble monomer aqueous solution:
Preparation 66ml mass percentage concentration is sodium acrylate-acrylamide solution of 35%, sodium acrylate and acrylamide mass ratio are 2: 1, to wherein adding 0.258g linking agent N,N methylene bis acrylamide, stirring and dissolving feeds high purity nitrogen 30min simultaneously to get rid of the oxygen in the solution.Dissolving after-filtration solution adds initiator potassium persulfate 0.0773g, stirring and dissolving again in solution.In solution, add 1.16gTX-10, stirring and dissolving again.
2, the emulsification of unsaturated polyester resin and curing:
Take by weighing the 154g unsaturated polyester, make it to react completely, add 4.62gSPAN-80 again, stir with the unsaturated polyester carboxyl terminal to wherein adding the stirring of 7.7g trolamine.The unsaturated water-soluble monomer aqueous solution that has prepared is slowly poured in the unsaturated polyester, constantly stirred with glass stick simultaneously, make the aqueous solution and unsaturated polyester form emulsion.The high-shear emulsion machine of using 10000r/min was to the further emulsification 3-5 of emulsion minute, in this emulsion process because the big mulser rotating speed of emulsion viscosity height, cause emulsion constantly to heat up, need to insert the thermometer monitoring and make emulsion temperature be no more than 50 ℃, avoid monomer in the aqueous solution to react too early and form hydrogel.After emulsification finishes,, and be cooled to room temperature with the bubble in the ultrasonic wave eliminating emulsion.Add the 7.7g benzoyl peroxide and stick with paste (50% mass concentration), dissolving stirs, add 1.6gN again, accelerine solution (20% mass concentration) stirs, slowly water and cast from the silicon rubber mould, this process should prevent to bubble and produce, and is placed on sheet glass to begin on the mould to solidify 24 hours.The aqueous gel unsaturated polyester that taking-up has cured places 60 ℃ of baking ovens to make water residual monomer complete reaction in 4 hours.Make hydrogel-containing unsaturated polyester resin composite sample HCUP-2.
Embodiment 9.A kind of preparation method of moisture unsaturated polyester resin composite material, step is as follows:
1, measures the 66ml deionized water, again to wherein adding the 1.16gTX-10 stirring and dissolving.
2, the emulsification of moisture unsaturated polyester resin and curing:
Take by weighing the 154g unsaturated polyester, make it to react completely, add 4.62gSPAN-80 again, stir with the unsaturated polyester carboxyl terminal to wherein adding the stirring of 7.7g trolamine.The unsaturated water-soluble monomer aqueous solution that has prepared is slowly poured in the unsaturated polyester, constantly stirred with glass stick simultaneously, make the aqueous solution and unsaturated polyester form emulsion.The high-shear emulsion machine of using 10000r/min was to the further emulsification 3-5 of emulsion minute, in this emulsion process because the big mulser rotating speed of emulsion viscosity height, cause emulsion constantly to heat up, need to insert the thermometer monitoring and make emulsion temperature be no more than 50 ℃, avoid monomer in the aqueous solution to react too early and form hydrogel.After emulsification finishes,, and be cooled to room temperature with the bubble in the ultrasonic wave eliminating emulsion.Add the 7.7g benzoyl peroxide and stick with paste (50% mass concentration), dissolving stirs, add 1.6gN again, accelerine solution (20% mass concentration) stirs, slowly water and cast from the silicon rubber mould, this process should prevent to bubble and produce, and is placed on sheet glass to begin on the mould to solidify 24 hours.The aqueous gel unsaturated polyester that taking-up has cured places 60 ℃ of baking ovens to make water residual monomer complete reaction in 4 hours.Make hydrogel-containing unsaturated polyester resin composite sample WCUP.
The test of embodiment 7～9 performance of composites is as follows:
With embodiment 9 moisture unsaturated polyester resin sample WCUP is contrast, measure prepared aqueous gel unsaturated polyester composite HCUP-1 of the embodiment of the invention 7,8 and oxygen index, mechanical property, tensile yield, water retention, the dimensional stability of HCUP-2 according to national standard, it is as shown in the table respectively for the result.
| ?WCUP | ?HCUP-1 | ?HCUP-2 | |
| Oxygen index | ?28 | ?34 | ?29 |
| Tensile strength/MP | ?13.36 | ?24.41 | ?22.54 |
| Flexural strength/MP | ?16.16 | ?24.7 | ?33.73 |
| Shock strength/KJ/m-2 | ?1.7 | ?1.67 | ?3.33 |
| Tensile yield/% | ?1.297 | ?2.566 | ?1.685 |
| Water retention/% | ?70.7 | ?89.4 | ?73.4 |
| Size retention rate/% | ?97.06 | ?99.29 | ?97.72 |
Test result shows that HCUP-1 and HCUP-2 increase at all properties with respect to WCUP, improves more obvious with the HCUP-1 over-all properties.
Claims (9)
1. hydrogel-containing unsaturated polyester resin flame-retardant composite material, comprise moisture unsaturated polyester resin, it is characterized in that its mass parts component is as follows: unsaturated polyester resin 100, emulsifying agent 0-20, unsaturated polyester solidifying agent 0.5-3, unsaturated polyester promotor 0.05-1.5, aqueous polymerization initiator 0-2, aqueous polymerization linking agent 0-5, water-soluble monomer 1-50, water 50-100, wherein unsaturated monomer solution is by the unsaturated monomer and the initiator thereof that can carry out radical polymerization, linking agent, water and emulsifying agent are formed, and the quality percentage composition of unsaturated monomer is 1-50% in the unsaturated monomer solution.
2. according to the described hydrogel-containing unsaturated polyester resin flame-retardant composite material of claim 1, it is characterized in that said water-soluble monomer is one or more the monomeric mixtures among sodium acrylate, vinylformic acid, acrylamide, methylene-succinic acid, MALEIC ANHYDRIDE, 2-acrylamido-2 methyl propane sulfonic acid AMPS or the methylacryoyloxyethyl trimethyl ammonium chloride DMC, is preferably sodium acrylate.
3. according to claim 1 or 2 described hydrogel-containing unsaturated polyester resin flame-retardant composite materials, it is characterized in that said emulsifying agent is that in SPAN-60, SPAN-80, SPAN-85, TWEEN-80, TX-10, trolamine, sodium hydroxide, the magnesium oxide one or more are united use, is preferably SPAN-80 and TX-10 or SPAN-80 and trolamine.
4. according to the described hydrogel-containing unsaturated polyester resin flame-retardant composite material of claim 3, it is characterized in that said aqueous polymerization initiator is a kind of of Potassium Persulphate, ammonium persulphate, Sodium Persulfate, is preferably Potassium Persulphate.
5. according to the described hydrogel-containing unsaturated polyester resin flame-retardant material of claim 4, it is characterized in that said aqueous polymerization linking agent is a N,N methylene bis acrylamide.
6. according to the described hydrogel-containing unsaturated polyester resin flame-retardant composite material of claim 5, it is characterized in that said solidifying agent is dibenzoyl peroxide or diphenyl peroxide ketone, is preferably dibenzoyl peroxide; Promotor is N, and accelerine, cobalt naphthenate one or both of mixture is preferably N, accelerine.
7. according to the preparation method of the described hydrogel-containing unsaturated polyester resin flame-retardant composite material of claim 1, it is characterized in that comprising the steps:
(1) linking agent is dissolved in the aqueous solution of water-soluble monomer, logical simultaneously nitrogen deoxygenation 30 minutes filters; In the solution after filtering, must concentration be the water-soluble monomer aqueous solution of 1-50% with initiator and emulsifiers dissolve again;
(2) emulsification of hydrogel-containing unsaturated polyester resin: in unsaturated polyester resin, the unsaturated water-soluble monomer aqueous solution that (1) is prepared slowly adds in the unsaturated polyester resin, carries out emulsification with high-shearing dispersion emulsifying machine simultaneously with emulsifiers dissolve;
(3) curing of hydrogel-containing unsaturated polyester resin: in the unsaturated polyester resin emulsion, add solidifying agent and promotor curing, unsaturated polyester resin composite material after solidifying placed under room temperature or 50-70 ℃ of temperature continue reaction 1-5 hour, obtain the hydrogel-containing unsaturated polyester resin matrix material.
8. according to the preparation method of the described hydrogel-containing unsaturated polyester resin flame-retardant composite material of claim 7, it is characterized in that step (3) also process degassing before curing, the degassing is to adopt ultrasonic degas or vacuum outgas, and solidification value is 20-35 ℃, and be 5-20 minute set time.
9. according to the preparation method of the described hydrogel-containing unsaturated polyester resin flame-retardant composite material of claim 8, it is characterized in that the water-soluble monomer in the inverse emulsion utilizes curable unsaturated polyester generation heat that cross-linking polymerization takes place simultaneously.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181014A (en) * | 2011-03-25 | 2011-09-14 | 天地科技股份有限公司 | Bi-component flame-retardant low-viscosity unsaturated polyester resin and preparation method thereof |
| CN106493827A (en) * | 2016-10-12 | 2017-03-15 | 浙江农林大学 | A kind of engineered wood and preparation method thereof |
| CN107384283A (en) * | 2017-07-31 | 2017-11-24 | 常州聚盛节能工程有限公司 | A kind of high-strength cloud stone glue |
| CN110156926A (en) * | 2019-06-04 | 2019-08-23 | 北京理工大学 | Low-density foamed hydrogel pad and preparation method thereof, extinguishing device |
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2007
- 2007-12-05 CN CNA2007101152552A patent/CN101225215A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181014A (en) * | 2011-03-25 | 2011-09-14 | 天地科技股份有限公司 | Bi-component flame-retardant low-viscosity unsaturated polyester resin and preparation method thereof |
| CN102181014B (en) * | 2011-03-25 | 2013-03-20 | 天地科技股份有限公司 | Bi-component flame-retardant low-viscosity unsaturated polyester resin and preparation method thereof |
| CN106493827A (en) * | 2016-10-12 | 2017-03-15 | 浙江农林大学 | A kind of engineered wood and preparation method thereof |
| CN107384283A (en) * | 2017-07-31 | 2017-11-24 | 常州聚盛节能工程有限公司 | A kind of high-strength cloud stone glue |
| CN110156926A (en) * | 2019-06-04 | 2019-08-23 | 北京理工大学 | Low-density foamed hydrogel pad and preparation method thereof, extinguishing device |
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